CN104846400B - A kind of electrolysis device based on electrowetting principle on dielectric layer and preparation method thereof - Google Patents
A kind of electrolysis device based on electrowetting principle on dielectric layer and preparation method thereof Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于数字微流控技术领域,涉及基于介质层上电润湿原理的微流控技术及液体的电解过程,具体涉及一种基于介质层上电润湿原理的电解器件。The invention belongs to the technical field of digital microfluidics, and relates to a microfluidic technology based on the principle of electrowetting on a medium layer and an electrolysis process of a liquid, in particular to an electrolytic device based on the principle of electrowetting on a medium layer.
背景技术Background technique
芯片实验室可简单定义为能够完成生物化学处理的各个过程、能自动完成传统实验室功能的微小化、集成化微电子机械系统,其目标是在单个器件上集成完全的分析过程,具有高集成度、高精度、低消耗、智能化等优点,在生物、化学等许多领域具有非常好的前景。Lab-on-a-chip can be simply defined as a miniaturized and integrated micro-electro-mechanical system that can complete various processes of biochemical processing and automatically complete traditional laboratory functions. Its goal is to integrate a complete analysis process on a single device, with high integration High-precision, high-precision, low-consumption, intelligent and other advantages, it has very good prospects in many fields such as biology and chemistry.
作为芯片实验室的动力部分,微流控技术起着重要作用。介质上电润湿技术通过电压改变液滴在介质表面的润湿性能以对液滴进行操控,具有驱动方式简单、驱动力强、自动化程度高等许多优点,但存在功能单一、集成度低等不足。As the power part of lab-on-a-chip, microfluidic technology plays an important role. The electrowetting technology on the medium changes the wettability of the droplet on the surface of the medium by voltage to control the droplet. It has many advantages such as simple driving method, strong driving force, and high degree of automation, but it has disadvantages such as single function and low integration. .
电解在生物、化学等诸多领域中均为常用技术,而现有的电解手段大多存在产生气泡、电解产物分布不均匀、电解反应程度控制不精确、工艺条件严格、试剂用量大等问题,极大地限制了其在便携设备及芯片实验室等领域的应用。因此在数字微流控芯片中实现电解功能的集成有着极其重要的意义。Electrolysis is a commonly used technology in many fields such as biology and chemistry, but most of the existing electrolysis methods have problems such as bubble generation, uneven distribution of electrolysis products, inaccurate control of the degree of electrolysis reaction, strict process conditions, and large amount of reagents. It limits its application in fields such as portable equipment and lab-on-a-chip. Therefore, it is of great significance to realize the integration of electrolysis function in the digital microfluidic chip.
发明内容Contents of the invention
本发明的目的在于提供一种能够精准产生定量电解产物并将氧化产物与还原产物分割于不同液滴,同时又能够与现有微流控技术相兼容的集成化数字微流控芯片,进而在改进现有电解功能器件的基础上扩大数字微流控技术的应用范围。The purpose of the present invention is to provide an integrated digital microfluidic chip that can accurately generate quantitative electrolytic products and divide the oxidized products and reduced products into different droplets, and is compatible with the existing microfluidic technology. Expand the application range of digital microfluidic technology on the basis of improving the existing electrolytic functional devices.
为达到上述目的,本发明提供了一种基于介质层上电润湿原理的电解器件,该电解器件包含:To achieve the above object, the present invention provides an electrolytic device based on the principle of electrowetting on a dielectric layer, the electrolytic device comprising:
下极板,该下极板由第一衬底、电极层、介质层、第一疏水层从下到上依次设置构成;及a lower pole plate, the lower pole plate is composed of a first substrate, an electrode layer, a dielectric layer, and a first hydrophobic layer arranged in sequence from bottom to top; and
上极板,该上极板由第二衬底、接地电极和第二疏水层从上到下依次设置构成;An upper plate, the upper plate is composed of a second substrate, a ground electrode and a second hydrophobic layer arranged in sequence from top to bottom;
待电解液滴D置于第一疏水层与第二疏水层之间;其中,所述的电极层包含若干电解电极和若干驱动电极,电极两两之间电气隔离;所述电解电极嵌入设置在驱动电极中,将电解功能集成入数字微流控器件,并能实现电解产物的隔离。所述电解电极的“嵌入”指的是电解电极被数字微流芯片驱动电极包围但电气隔离,且电极是处于同一个平面上。The electrolytic liquid drop D is placed between the first hydrophobic layer and the second hydrophobic layer; wherein, the electrode layer includes several electrolytic electrodes and several driving electrodes, and the electrodes are electrically isolated between two electrodes; the electrolytic electrodes are embedded in the In the driving electrode, the electrolysis function is integrated into the digital microfluidic device, and the isolation of the electrolysis product can be realized. The "embedding" of the electrolysis electrodes means that the electrolysis electrodes are surrounded but electrically isolated by the driving electrodes of the digital microfluidic chip, and the electrodes are on the same plane.
所述驱动电极、电解电极的形状、大小以及其“嵌入”位置并不严格限定,以实现其功能为设计准则,但电解电极尺寸在能够实现电解功能的条件下应尽量小,能够被驱动电极包围,以实现液滴能够被运输并被电解电极接触电解,而将液滴运输离开时电极上没有液体残留。The shape, size and "embedded" position of the driving electrode and the electrolysis electrode are not strictly limited, and the design criterion is to realize its function, but the size of the electrolysis electrode should be as small as possible under the condition that the electrolysis function can be realized, and can be driven by the electrode. Surrounded so that the droplets can be transported and electrolyzed by the electrolysis electrodes, and there is no liquid residue on the electrodes when the droplets are transported away.
所述待电解“液滴”是指能用于介质层上电润湿驱动的液滴,其成分并不限定,可以是单一的生物样品,也可以是多成分组成;同时其大小也不限定,考虑到液滴驱动结构的限制最好为皮升到若干毫升之间。The "droplet" to be electrolyzed refers to the droplet that can be used for electrowetting on the dielectric layer, and its composition is not limited, it can be a single biological sample, or it can be composed of multiple components; at the same time, its size is not limited , considering the limitations of the droplet-driven structure, it is best to be between picoliters and several milliliters.
上述的电解器件,其中,所述的电解电极由电解阳极Ep和电解阴极En组成,并被若干驱动电极隔开。The above electrolysis device, wherein the electrolysis electrodes are composed of electrolysis anode E p and electrolysis cathode E n , and are separated by several driving electrodes.
上述的电解器件,其中,所述电解阳极Ep和电解阴极En裸露设置,能与待电解液滴D直接接触。电解电极上不覆盖介质层和疏水层,通过数字微流自动化操控方法将液滴运输到电解电极实现自动化电解与液滴分裂以增强电解电极的工作效率。The electrolysis device above, wherein the electrolysis anode E p and the electrolysis cathode En are exposed and can be in direct contact with the droplet D to be electrolyzed. The electrolysis electrode is not covered with the dielectric layer and the hydrophobic layer, and the liquid droplets are transported to the electrolysis electrode through the digital microflow automatic control method to realize automatic electrolysis and droplet splitting to enhance the working efficiency of the electrolysis electrode.
上述的电解器件,其中,所述的电解电极和驱动电极均为平面电极。In the above electrolysis device, the electrolysis electrodes and the driving electrodes are planar electrodes.
上述的电解器件,其中,所述的电解电极和驱动电极的上下表面均处于同一平面。In the above electrolysis device, the upper and lower surfaces of the electrolysis electrode and the driving electrode are on the same plane.
上述的电解器件,其中,所述的第一衬底、第二衬底采用绝缘材料。In the above electrolytic device, the first substrate and the second substrate are made of insulating materials.
上述的电解器件,其中,所述的介质层材料选择具有一定介电常数与抗击穿能力的不导电物质,优选介电常数高且抗击穿能力强的物质,包括但不限于脂环族环氧树脂CEP、SU-8、五氧化二钽等。The above-mentioned electrolytic device, wherein, the material of the dielectric layer is a non-conductive substance with a certain dielectric constant and breakdown resistance, preferably a substance with a high dielectric constant and strong breakdown resistance, including but not limited to alicyclic epoxy Resin CEP, SU-8, tantalum pentoxide, etc.
上述的电解器件,其中,所述的第一疏水层、第二疏水层的材料选择能够降低液滴表面张力的材料,包括但不限于特氟龙Teflon、氟树脂Cytop等。In the above-mentioned electrolytic device, the materials of the first hydrophobic layer and the second hydrophobic layer are selected to reduce the surface tension of the droplet, including but not limited to Teflon, Cytop, and the like.
本发明还提供了一种基于介质层上电润湿原理的电解器件的制备方法,该方法包含:The present invention also provides a method for preparing an electrolytic device based on the principle of electrowetting on a dielectric layer, the method comprising:
步骤1,制备下极板:在第一衬底制备包含若干驱动电极和电解电极的电极层,其中,电解电极嵌入在驱动电极中;在电极层上制备介质层;在介质层上制备第一疏水层,并使得电解电极裸露于介质层和第一疏水层;Step 1, preparing the lower plate: preparing an electrode layer including several driving electrodes and electrolytic electrodes on the first substrate, wherein the electrolytic electrodes are embedded in the driving electrodes; preparing a dielectric layer on the electrode layer; preparing a first electrode layer on the dielectric layer Hydrophobic layer, and make the electrolysis electrode exposed to the medium layer and the first hydrophobic layer;
步骤2,制备上极板:在第二衬底上制备接地电极,再制备第二疏水层;Step 2, preparing the upper plate: preparing a ground electrode on the second substrate, and then preparing a second hydrophobic layer;
步骤3,将上极板、下极板组装形成所述的基于介质层上电润湿原理的电解器件。Step 3, assembling the upper plate and the lower plate to form the electrolytic device based on the principle of electrowetting on the dielectric layer.
本发明以介质层上电润湿原理为基础,提出了一种将电解功能集成于数字微流控芯片结构的新型微流控器件,通过控制数字微流控芯片中的液滴输运、液滴分裂与电解等过程对液滴进行操作,从而产生含有不同电解产物的液滴。Based on the principle of electrowetting on the dielectric layer, the present invention proposes a new type of microfluidic device that integrates the electrolysis function into the structure of the digital microfluidic chip. Processes such as droplet splitting and electrolysis operate on droplets to generate droplets containing different electrolysis products.
本发明提供的基于介质层上电润湿原理的电解集成数字微流控芯片具有如下优势:The electrolytic integrated digital microfluidic chip based on the principle of electrowetting on the dielectric layer provided by the present invention has the following advantages:
a)电解电极集成到数字微流控芯片驱动电极中,精简了芯片结构,简化了制作工艺。a) The electrolytic electrode is integrated into the driving electrode of the digital microfluidic chip, which simplifies the chip structure and simplifies the manufacturing process.
b)液滴输运及电解过程可以完全自动化,速度快,通量高,有利于含电解产物液滴的大量快速生成,并实现对液滴内部电解产物浓度的精准控制。b) The droplet transportation and electrolysis process can be fully automated, fast, and high throughput, which is conducive to the rapid generation of a large number of droplets containing electrolysis products, and realizes precise control of the concentration of electrolysis products inside the droplets.
c)电解电极只占到芯片的一小部分,有利于更多功能的集成及芯片的便携式应用,拓展了数字微流控芯片的应用范围。c) The electrolytic electrode only occupies a small part of the chip, which is conducive to the integration of more functions and the portable application of the chip, and expands the application range of the digital microfluidic chip.
附图说明Description of drawings
图1是本发明的基于介质层上电润湿原理的电解器件的结构示意图(纵向剖面图)。Fig. 1 is a structural schematic view (longitudinal sectional view) of an electrolytic device based on the principle of electrowetting on a dielectric layer according to the present invention.
图2是本发明的基于介质层上电润湿原理的电解器件的下极板电极配置原理性示意图。Fig. 2 is a schematic diagram of the electrode configuration of the lower plate of the electrolytic device based on the principle of electrowetting on the dielectric layer according to the present invention.
具体实施方式detailed description
以下结合附图通过具体实施例对本发明作进一步的描述,这些实施例仅用于说明本发明,并不是对本发明保护范围的限制。The present invention will be further described below through specific embodiments in conjunction with the accompanying drawings. These embodiments are only used to illustrate the present invention, and are not intended to limit the protection scope of the present invention.
本发明提供的基于介质层上电润湿原理的电解器件是通过电极设计和驱动信号控制来实现的,因此可以有多种配置方式,可以配置于各种数字微流芯片中。The electrolytic device based on the principle of electrowetting on the dielectric layer provided by the present invention is realized through electrode design and driving signal control, so it can be configured in various ways and can be configured in various digital microfluidic chips.
本发明的原理性结构示意图(纵向剖面图)如图1所示。在绝缘的第一衬底100上为本发明的驱动电极E1-E6和电解电极Ep和En,其中电解电极Ep和En分别嵌入到驱动电极E3和E5当中,但两两之间电气隔离。用作衬底的材料并不固定,只要绝缘即可;电解电极材料应为满足电解要求的金属,而数字微流驱动电极(包括上极板电极,即接地电极105)原则上可以由任何导电材料组成,但为了简化芯片制作工艺,优选为与电解电极一致的材料;所有电极的大小、间隔及个数并不限定,本说明书仅以一定数目及规格的电极为例;文末附图只为原理性示意图,并不精确反应电极的位置及排布。The schematic structural diagram (longitudinal section view) of the present invention is shown in FIG. 1 . On the insulating first substrate 100 are the driving electrodes E1-E6 and the electrolysis electrodes Ep and En of the present invention, wherein the electrolysis electrodes Ep and En are respectively embedded in the driving electrodes E3 and E5, but are electrically isolated from each other. The material used as the substrate is not fixed, as long as it is insulated; the electrolysis electrode material should be a metal that meets the electrolysis requirements, and the digital micro-flow driving electrode (including the upper plate electrode, that is, the ground electrode 105) can be made of any conductive material in principle. Composition of materials, but in order to simplify the chip manufacturing process, it is preferably the same material as the electrolysis electrodes; the size, interval and number of all electrodes are not limited, this specification only takes a certain number and specifications of electrodes as an example; the drawings at the end of the article are only The schematic diagram does not accurately reflect the position and arrangement of the electrodes.
在电极上设有介质层102,其上设有疏水层103。第一衬底100、电极层101、介质层102及第一疏水层103共同构成了器件下极板201。在下极板201上放置驱动的液滴D,液滴之上为第二疏水层104,第二疏水层104上有接地电极105,其上为绝缘的第二衬底106。接地电极105的材料并不限定,但为了扩展芯片功能集成,优选为导电透明材料,如氧化铟锡(ITO)、掺铝的氧化锌(AZO)等。第二疏水层104、接地电极105、第二衬底106共同构成了器件的上极板202。A dielectric layer 102 is provided on the electrodes, and a hydrophobic layer 103 is provided thereon. The first substrate 100 , the electrode layer 101 , the dielectric layer 102 and the first hydrophobic layer 103 together constitute the lower plate 201 of the device. The driven droplet D is placed on the lower plate 201 , the second hydrophobic layer 104 is placed on the droplet, the ground electrode 105 is on the second hydrophobic layer 104 , and the insulating second substrate 106 is on the second hydrophobic layer 104 . The material of the ground electrode 105 is not limited, but in order to expand the integration of chip functions, it is preferably a conductive transparent material, such as indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), and the like. The second hydrophobic layer 104 , the ground electrode 105 and the second substrate 106 together constitute the upper plate 202 of the device.
本发明中电解电极必须裸露以使溶液能够接触电解电极进行电解,即电解电极上方的102介质层和103疏水层必须去掉。实际制备中,可采用光刻刻蚀或机械方法等同时去除两层材料,也可以在制备疏水层103前先去除电解电极上的介质层102,其后使用光刻刻蚀或剥离(lift-off)等方法去掉电解电极上的疏水层103。在本发明中,通过对驱动电极施加电压控制信号而接地电极接地即可对上下极板间的液滴D进行驱动,而将电解电极En和Ep引出即可进行电解操作。In the present invention, the electrolysis electrodes must be exposed so that the solution can contact the electrolysis electrodes for electrolysis, that is, the 102 dielectric layer and the 103 hydrophobic layer above the electrolysis electrodes must be removed. In actual preparation, photolithography or mechanical methods can be used to remove the two layers of materials at the same time, or the dielectric layer 102 on the electrolytic electrode can be removed before the hydrophobic layer 103 is prepared, and then photolithography or stripping (lift- off) and other methods to remove the hydrophobic layer 103 on the electrolysis electrode. In the present invention, the droplet D between the upper and lower plates can be driven by applying a voltage control signal to the drive electrode and the ground electrode is grounded, and the electrolysis operation can be performed by drawing out the electrolysis electrodes En and Ep.
本发明的电极配置原理示意如图2所示,传统介质层上电润湿结构的相间隔驱动电极上分别嵌入电解阴极与电解阳极(En,Ep),由这五个电极协作完成液滴分裂、电解与电解产物的隔离。通过输运过程使得电极E1-E3上方承载液滴,此时这三个驱动电极均施加有效驱动电压,随后在电解电极En和Ep上分别施加电性相反的电解电压对液体进行电解,当电解过程结束后将电极E2接地使液体从中部断裂从而形成分别含有还原产物与氧化产物的两个液滴。应当指出,上述仅为本发明的原理性说明,允许在不影响其功能性的前提下对器件结构及用途进行改进与拓展。The schematic diagram of the electrode configuration principle of the present invention is shown in Figure 2. The electrolytic cathode and electrolytic anode (E n , E p ) are respectively embedded in the spaced driving electrodes of the electrowetting structure on the traditional dielectric layer, and these five electrodes cooperate to complete the liquid Droplet splitting, electrolysis and isolation of electrolysis products. The liquid droplets are carried on the electrodes E1-E3 through the transport process. At this time, the three driving electrodes are all applied with effective driving voltages, and then the electrolysis voltages with opposite electrical properties are applied to the electrolysis electrodes En and Ep to electrolyze the liquid. When the electrolysis After the process is completed, the electrode E2 is grounded to break the liquid from the middle to form two droplets containing the reduced product and the oxidized product respectively. It should be pointed out that the above is only a schematic illustration of the present invention, and it is allowed to improve and expand the structure and application of the device without affecting its functionality.
本发明中,所述驱动电极施加电压(加电)是指芯片实施液滴操控时对应电极的电压被置成不为0以使电润湿驱动能够发生。In the present invention, the voltage application (power-on) of the drive electrodes refers to that the voltage of the corresponding electrodes is set to be non-zero when the chip implements droplet manipulation, so that the electrowetting drive can occur.
本发明中,所述电解电极施加电压(加电)是指芯片实施液滴操控时对应电解电极的电压被置成不为0以使电解过程能够发生。In the present invention, the voltage application (power-on) of the electrolysis electrodes refers to that the voltage corresponding to the electrolysis electrodes is set to be non-zero when the chip implements droplet manipulation so that the electrolysis process can occur.
本发明中,所述“接地”是指芯片实施液滴操控时对应电极的电压被置成0或与0足够接近。In the present invention, the "grounding" means that the voltage of the corresponding electrode is set to 0 or sufficiently close to 0 when the chip implements droplet manipulation.
结合图1、图2,本发明的电解集成数字微流控芯片的一种可实施的制备工艺如下:With reference to Fig. 1 and Fig. 2, a possible preparation process of the electrolytic integrated digital microfluidic chip of the present invention is as follows:
步骤1,下极板绝缘第一衬底100上采用旋涂、蒸发、溅射等工艺形成金属薄膜,通过光刻刻蚀方法形成驱动电极和集成电解电极;Step 1, forming a metal film on the lower plate insulation first substrate 100 by spin coating, evaporation, sputtering and other processes, and forming a driving electrode and an integrated electrolytic electrode by photolithography;
步骤2,通过旋涂、物理溅射、化学气相沉积等方法制备绝缘介质层,通过光刻刻蚀方法形成集成电化学电极上的“凹坑”以裸露电解电极。应当指出,如果介质层材料为如SU-8等特殊材料,采用一步光刻成膜方法即可形成所需结构;In step 2, an insulating dielectric layer is prepared by methods such as spin coating, physical sputtering, and chemical vapor deposition, and a "pit" on the integrated electrochemical electrode is formed by photolithography to expose the electrolytic electrode. It should be pointed out that if the material of the dielectric layer is a special material such as SU-8, the required structure can be formed by one-step photolithography film formation method;
步骤3,通过旋涂、蒸发、溅射成膜等方法制备疏水层,通过光刻刻蚀方法去掉电解电极表面的部分。此外,可以采用剥离工艺(lift off),即先光刻图形,其后形成疏水层,再通过剥离方法去掉不需要部分,也可以在薄膜制备过程中不对绝缘介质层和疏水层进行光刻刻蚀而在制备完成后使用机械手段使电解电极暴露;Step 3, preparing a hydrophobic layer by methods such as spin coating, evaporation, and sputtering to form a film, and removing the surface of the electrolytic electrode by photolithography. In addition, the lift off process (lift off) can be used, that is, the photolithographic pattern is first formed, and then the hydrophobic layer is formed, and then the unnecessary part is removed by the lift off method, and the insulating dielectric layer and the hydrophobic layer can not be photolithographically etched during the film preparation process. etch to expose the electrolytic electrodes by mechanical means after preparation;
步骤,4,上极板在绝缘第二衬底106上通过旋涂、蒸发、溅射等工艺形成金属薄膜形成接地电极105,其后通过旋涂、溅射等方法制备第二疏水层104;Step 4, the upper plate is formed on the insulating second substrate 106 by spin coating, evaporation, sputtering and other processes to form a metal film to form the ground electrode 105, and then the second hydrophobic layer 104 is prepared by spin coating, sputtering and other methods;
步骤5,将上极板、下极板组装形成数字微流控芯片。自此,本发明的基于介质层上电润湿原理的新型电解器件制备完成,将其与其他微流控器件相结合后,采用数字微流控操作方法即可自动化实现溶液的各种操作及传感。Step 5, assembling the upper plate and the lower plate to form a digital microfluidic chip. Since then, the preparation of the novel electrolytic device based on the principle of electrowetting on the dielectric layer of the present invention has been completed. After combining it with other microfluidic devices, the digital microfluidic operation method can be used to automatically realize various operations and operations of the solution. sensing.
本申请的核心原创点在于将暴露的电极用于液体电解,且与EWOD(electrowetting-on-dielectrics,介质上电润湿)液滴产生过程结合从而实现了电解产物的隔离。具体来说,本发明提供的电解器件的驱动电极上覆盖了绝缘介质层和疏水层,而电解电极上方的介质层和疏水层被去掉,以使得电解电极“裸露”;待电解液滴通过介质层上电润湿原理经驱动电极输运到集成电解电极上方,接触到电解电极进行电解,生成的含有电解产物的液滴,随后被运输离开电解电极,从而实现自动化操控。The core original point of this application is that the exposed electrodes are used for liquid electrolysis, and combined with the EWOD (electrowetting-on-dielectrics, electrowetting on medium) droplet generation process to achieve the isolation of electrolysis products. Specifically, the driving electrode of the electrolytic device provided by the present invention is covered with an insulating medium layer and a hydrophobic layer, and the dielectric layer and the hydrophobic layer above the electrolytic electrode are removed so that the electrolytic electrode is "bare"; The electrowetting principle on the layer is transported to the top of the integrated electrolysis electrode through the driving electrode, and it contacts the electrolysis electrode for electrolysis, and the generated liquid droplets containing electrolysis products are then transported away from the electrolysis electrode, thereby realizing automatic control.
本发明的电解器件同样适用于不需隔离电解产物的用途,此时仅进行电解过程而不进行液滴分裂操作。The electrolysis device of the present invention is also suitable for applications where isolation of the electrolysis product is not required, in which case only the electrolysis process is performed and no droplet splitting operation is performed.
尽管本发明的内容已经通过上述优选实施例作了详细介绍,但应当认识到上述的描述不应被认为是对本发明的限制。在本领域技术人员阅读了上述内容后,对于本发明的多种修改和替代都将是显而易见的。因此,本发明的保护范围应由所附的权利要求来限定。Although the content of the present invention has been described in detail through the above preferred embodiments, it should be understood that the above description should not be considered as limiting the present invention. Various modifications and alterations to the present invention will become apparent to those skilled in the art upon reading the above disclosure. Therefore, the protection scope of the present invention should be defined by the appended claims.
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